CN112957932B - Preparation and application of amphiphilic graft copolymer homogeneous-pore ultrafiltration membrane with high permeability and pH response - Google Patents

Preparation and application of amphiphilic graft copolymer homogeneous-pore ultrafiltration membrane with high permeability and pH response Download PDF

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CN112957932B
CN112957932B CN202110204144.9A CN202110204144A CN112957932B CN 112957932 B CN112957932 B CN 112957932B CN 202110204144 A CN202110204144 A CN 202110204144A CN 112957932 B CN112957932 B CN 112957932B
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朱小萤
叶其胜
王睿
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Zhejiang University ZJU
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/78—Graft polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
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Abstract

The invention discloses an amphiphilic graft copolymer homogeneous pore ultrafiltration membrane with pH response, a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) amphiphilic graft copolymers having pH response are prepared by grafting hydrophilic monomers onto hydrophobic polymers by Atom Transfer Radical Polymerization (ATRP). 2) Directly preparing the pH response amphiphilic graft copolymer homogeneous-pore ultrafiltration membrane by a non-solvent phase inversion method. The invention has simple process and can realize large-scale industrial production. The pH-responsive amphiphilic pore-equalizing filter membrane prepared by the invention adopts amphiphilic graft copolymer micelle self-assembly to prepare a membrane, and has narrower pore size distribution and higher selectivity and permeability. In addition, this pore-equalizing filter membrane has higher antipollution and can effectively filter the nanometer plastics, can carry out effectual aperture regulation and control between pH 3 ~ 11, realizes that the grading of pollutant is held back and the screening is retrieved.

Description

Preparation and application of amphiphilic graft copolymer homogeneous-pore ultrafiltration membrane with high permeability and pH response
Technical Field
The invention belongs to the technical field of preparation of environment high polymer materials, designs an amphiphilic graft copolymer pore-equalizing filter membrane, and particularly relates to a preparation method of an amphiphilic graft copolymer membrane with a pH-responsive side chain as a hydrophilic section.
Background
With the increase of global population and the improvement of industrial level, the water demand is continuously increased, and the insufficient water supply becomes the resistance for restricting the social progress. Therefore, people pay attention to how to treat sewage efficiently and at low cost. In water treatment, the filter membrane can realize selective separation of substances with different micro scales under the drive of external drive, density difference or concentration difference. The membrane separation technology has the functions of energy conservation, simple and convenient operation, high efficiency, low cost and the like, and becomes one of the most rapidly developed and widely applied technologies in the field of water treatment at present.
Polyvinylidene fluoride filter membranes have the advantages of chemical stability resistance, oxidation resistance and the like in the application process, and are widely applied in the fields of water treatment, material separation and the like. But polyvinylidene fluoride has stronger hydrophobicity, so that the polyvinylidene fluoride is easy to pollute in the using process, and due to the limitation of a film forming material and a method, the effective aperture distribution of the filter membrane is wider, so that the selectivity is low, and the separation effect is poor, therefore, the amphiphilic graft copolymer is adopted for self-assembly preparation of the membrane, and the hydrophilic modification and uniform aperture of the membrane are realized. In addition, the current water treatment has diversified pollutants, and the pollutants of various types and different sizes restrict the wide application of the membrane technology. And a single filter membrane cannot accurately regulate and control the filtering of pollutants with different molecular scales. Stimuli responsive membranes allow self-regulation of pore size in response to ambient conditions (e.g. magnetic field, electric field, pH, temperature, light) which are widely used in chemical fields for controlled release of drugs, water treatment and sensors. The pH response membrane has lower energy consumption and simpler operation and is more suitable for actual water treatment.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to simply and easily prepare a high-flux anti-fouling pore-equalizing ultrafiltration membrane with pH responsiveness, and solve the problems of poor anti-fouling performance, low selectivity, insufficient control on membrane pores and nano plastic grading interception application of the traditional filter membrane.
The purpose of the invention is realized by the following technical scheme: a preparation method of an amphiphilic graft copolymer mesoporous ultrafiltration membrane with pH response comprises the steps of taking a hydrophobic polymer as a framework, preparing a pH response polymer through an ATRP (atom transfer radical polymerization) grafting monomer, and preparing the amphiphilic graft copolymer mesoporous ultrafiltration membrane with pH response through a non-solvent phase inversion method. The preparation method comprises the following steps:
dissolving a hydrophobic polymer, a monomer, a catalyst and a ligand into a first polar solvent to form a solution, wherein the ratio of the hydrophobic polymer to the monomer is 1: 2.6(g/m), the mass ratio of the hydrophobic polymer to the catalyst is 1:0.13, the volume ratio of the monomer to the ligand is 2.6:0.29, then the anhydrous and oxygen-free conditions are ensured through three cyclic operations of vacuumizing and nitrogen introduction, the solution is heated to 55-95 ℃ and stirred for 4-24 hours, then the solution is diluted to be not viscous to obtain a polymer solution, the polymer solution is dropwise added into a methanol-water mixed solution (volume 1:1) to be precipitated, the precipitate is collected by filtration, and the pH-responsive amphiphilic graft polymer is obtained by freeze drying to constant weight.
Dissolving pH-responsive amphiphilic graft polymer with the mass fraction of 12-18% in a second polar solvent, heating and stirring at 60 ℃ for 12-24 h, standing and defoaming to obtain a homogeneous casting solution; pouring the casting film liquid on a dry and clean glass plate uniformly, scraping a liquid film by a scraper at a constant speed, immersing the liquid film in a coagulating bath, preparing a pH response filter membrane by a non-solvent induced phase transition method, periodically changing water to remove the solvent, and immersing the prepared membrane in distilled water for later use.
Further, the hydrophobic polymer is a fluorine-containing high molecular polymer having one or more structures of C-H, C-Cl and C-Br, specifically polyvinylidene fluoride (PVDF), a vinylidene fluoride-chlorotrifluoroethylene copolymer (P (VDF-CTFE)), or a vinylidene fluoride-hexafluoropropylene copolymer (P (VDF-HFP)), and preferably a vinylidene fluoride-chlorotrifluoroethylene copolymer (P (VDF-CTFE)), as shown below.
Figure BDA0002949171520000021
Wherein: x is 1000 + 10000, and y is 100 + 1000.
Furthermore, the monomer is one of tert-butyl methacrylate, dimethylaminoethyl methacrylate and 4-vinylpyridine, and is preferably tert-butyl methacrylate.
Further, the catalyst is CuCl, CuBr, CuCl 2 、CuBr 2 Preferably CuCl, or a mixture thereof.
Further, the first polar solvent is one or a mixed solvent of N-methylpyrrolidone, N-dimethylformamide, N, N-dimethylacetamide and dimethylsulfoxide, and preferably N-methylpyrrolidone.
The ligand is one of N, N, N '-pentamethyldiethylenetriamine and tris- (N, N-dimethylaminoethyl) amine or a mixture thereof, and is preferably N, N, N' -pentamethyldiethylenetriamine. 7. The second polar solvent according to claim 1 is one or a mixture of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, and tetrahydrofuran, preferably N, N-dimethylformamide.
Furthermore, the polymerization degree of the chain length of the grafting side chain is 4-28.
The invention also provides an amphiphilic graft copolymer mesoporous ultrafiltration membrane with pH response and application of the amphiphilic graft copolymer mesoporous ultrafiltration membrane with pH response in the fields of pollutant grading interception and water treatment, wherein the pollutants are preferably homopolystyrene and polyvinylpyrrolidone.
As mentioned above, the preparation method of the pH response amphiphilic graft copolymer homogeneous pore ultrafiltration membrane has the following advantages:
1) the pH response amphiphilic graft copolymer is prepared by ATRP polymerization, and the method has the advantages of high operation efficiency, wide monomer using range, controllable product structure and narrow molecular weight distribution.
2) The membrane is prepared by self-assembly of the pH-responsive amphiphilic graft polymer, and because the hydrophilic side chains with pH response are arranged on the surface of the membrane inside the pore channel, the hydrophilicity of the membrane can be effectively improved, and the response performance is more obvious.
3) The filter membrane with the uniform pore structure is formed by the phase conversion and self-assembly of the amphiphilic graft polymer.
4) The invention regulates and controls the pore size change of the membrane by changing pH, can efficiently filter or recover substances with different sizes in a grading way, and has wide prospect in the fields of controlled release of medicines, substance recovery and water treatment.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of pH-responsive amphiphilic graft copolymer P (VDF-CTFE) -g-PMAA in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of a P (VDF-CTFE) filter membrane PPM-0 (in the figure (a)) and a pH-responsive amphiphilic graft copolymer (in the figure (b)) of a homoporous filter membrane PPM-1 in example 1;
FIG. 3 is a graph comparing the surface contact angles of the P (VDF-CTFE) filters PPM-C and PPM-0 and pH-responsive amphiphilic graft copolymer (PPM-1) homogeneous pore filter in example 1;
FIG. 4 is a graph showing the water flux of PPM-0 and PPM-1 as a function of pH in example 2;
FIG. 5 is a graph of the retention of PPM-1 to nanoplastic as a function of pH for example 2;
figure 6 is a graph of pore size distribution of PPM-1 at pH 3 and pH 11 in example 2.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and the accompanying drawings. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention, and unless otherwise indicated, all technical means used in the experiments herein belong to the technical means recognized in the art.
Example 1
In this embodiment, the preparation method of the pH-responsive amphiphilic graft copolymer mesoporous ultrafiltration membrane uses a hydrophobic polymer as a framework, prepares a pH-responsive polymer through an ATRP grafting monomer, and prepares an amphiphilic graft copolymer mesoporous ultrafiltration membrane with pH response through a non-solvent phase inversion method. The method comprises the following specific steps:
1. after dissolving 1g P (VDF-CTFE) in a Schlenk flask containing N-methylpyrrolidone, 130mg of CuCl, 2.6ml of t-butyl methacrylate (tBMA), 290. mu. l N, N, N' -pentamethyldiethylenetriamine were added, and freeze-thaw was repeated three times with nitrogen gas through a double-line tube to remove oxygen, and the reaction mixture was stirred for 5 hours while being heated to 65 ℃ under nitrogen gas, whereby the reaction mixture became very viscous. Thus, the polymerization was stopped by cooling to room temperature and exposure to air. The reaction mixture was diluted with acetone to a non-viscous state, passed through a neutral alumina column, then precipitated in methanol, and lyophilized to constant weight in vacuo to obtain P (VDF-CTFE) -g-PtBMA.
2. Adding P (VDF-CTFE) -g-PtBMA into toluene solution containing 10% P-toluenesulfonic acid by mass, mechanically stirring at 85 ℃ for 10h, fully hydrolyzing, pouring the mixture into water, filtering, and freeze-drying in vacuum to constant weight to obtain P (VDF-CTFE) -g-PMAA with pH response.
3. Mixing P (VDF-CTFE) -g-PMAA and N, N-dimethylformamide, stirring for 12h at 60 ℃ to prepare a homogeneous membrane casting solution with the mass concentration of 15%, standing and defoaming the membrane casting solution, uniformly pouring the membrane casting solution on a dry and clean glass plate, scraping the membrane casting solution into a size of 300 mu m by using a membrane scraping machine, volatilizing the membrane casting solution in air for 30s, and then parallelly placing the glass plate in a coagulating bath water bath at the temperature of 25 ℃ to obtain the amphiphilic graft copolymer pore-equalizing filter membrane PPM-1 with pH response.
Meanwhile, the embodiment also sets un-grafted P (VDF-CTFE) membranes PPM-C and PPM-0 as control groups, the preparation method of the membranes PPM-C and PPM-0 is the same as the step 3, but PEG is added in the preparation of M0 membrane casting solution as pore-forming agent.
After the preparation is finished, the three membranes are characterized in appearance, performance and the like, a BRUKER AVIII500M nuclear magnetic resonance spectrometer is used for characterizing the pH amphiphilic graft copolymer, an S-4800 type field emission scanning electron microscope is used for respectively observing the surfaces and the sections of the four membranes, and an OSA200-T Optical contact angle analyzer is used for measuring the water contact angles of the surfaces of the three membranes. The test analysis results obtained by the above characterization means are shown in FIGS. 1 to 3.
FIG. 1 is a nuclear magnetic hydrogen spectrum of pH-responsive amphiphilic graft copolymer P (VDF-CTFE) -g-PMAA, with a-COOH peak seen at 12.4ppm, indicating successful grafting of the pH-responsive PMAA.
FIG. 2 is a scanning electron micrograph of P (VDF-CTFE) filter PPM-0 (FIG. 2 (a)), and a scanning electron micrograph of pH-responsive amphiphilic graft copolymer (homo-porous filter PPM-1) (FIG. 2 (b)). In (a) of FIG. 2, the unmodified PPM-0 has heterogeneous membrane pores, while in (b) of FIG. 2, the modified PPM-1 has uniformly distributed P (VDF-CTFE) -g-PMAA micelles, which can form uniform membrane pores.
FIG. 3 is a comparison graph of contact angles of PPM-C, PPM-0 and PPM-1 surfaces of a P (VDF-CTFE) filter membrane, wherein the contact angle of PPM-1 after grafting hydrophilic PMAA is reduced, the hydrophilicity is improved, and the anti-fouling performance of the filter membrane can be effectively improved.
Example 2
To characterize the pH responsiveness of the membranes, application experiments were performed on the PPM-0, PPM-1 membranes prepared in example 1 using a dead-end filtration system. Before measuring the water flux of the membrane, the membrane was first soaked in aqueous solutions of different pH 3, 5, 7, 9, 11 for 30min to stabilize its surface properties and internal structure. In measuring the water flux, the membrane pressure was set to 1.5psi, the water flux over 40min was measured, and the stable value was finally recorded as the water flux of the membrane at that pH. To characterize the pH response reversibility of the membrane, the response membrane was subjected to a cyclic flux test at pH 11/3. The water flux test results are shown in fig. 4.
In order to further characterize the change of pH value to pore diameter, polyvinylpyrrolidone (PVP) with different molecular weights and polystyrene microspheres (PS) with different sizes are selected in experiments, and the interception performance of PPM under different pH values is evaluated. The molecular weight of PVP1 is 5.5kDa, Stokes radius is 5.1nm, the molecular weight of PVP2 is 360kDa, the Stokes radius is 9.3nm, the molecular weight of PVP3 is 1300kDa, the Stokes radius is 15.6nm, the size of PS1 is about 20nm, and the size of PS2 is about 30 nm. The concentrations were all 100mg/L, and the pH of the feed solutions was set at 3, 5, 7, 9, 11. The concentrations of PVP and PS microspheres were determined by uv spectrophotometer. The retention at different pH is shown in figure 5.
In order to characterize the pore size distribution of the homogeneous pore filter, the pore size of the PPM was calculated by equation (1), and the probability density function curve of the pore size distribution calculated from the retention rates of PVP and PS is shown in FIG. 6.
Figure BDA0002949171520000051
r p Is the Stokes radius of the solute, μ p Stokes radius at a rejection of 50%, σ p The rejection was 84.13% to 50% stokes radius ratio.
FIG. 4 is a graph of the water flux of PPM-0 and PPM-1 as a function of pH, the water flux of PPM-1 decreases with increasing pH and is more stable after four cycles, which is not observed with unmodified PPM-0. This is because when the pH is decreased, the carboxyl group on PMAA is protonated to form a hydrogen bond, and the molecular chain shrinks to enlarge the pore size. As the pH increases, the carboxyl groups repel the chains in the form of negative ions, and the pores in the membrane become smaller. This indicates that PPM-1 has excellent pH response properties.
FIG. 5 is a graph showing the change of PPM-1 in the rejection rate of nano-plastic with pH, and as the pH value increases, the rejection rate of PPM-1 to pollutants gradually increases, and the pore size of the membrane gradually decreases.
Fig. 6 is a pore size distribution diagram of PPM-1 at pH 3 and pH 11, and it was calculated by simulation that the pore size of PPM-1 was about 9.8nm at pH 3 and became 5.2nm at pH 11, and it was also seen from (c) in fig. 6 that the pore size distribution of the membrane was narrow, indicating that it had a good mesopore structure.
The pH-responsive amphiphilic graft copolymer uniform-pore ultrafiltration membrane prepared by the invention solves the problems that the effective pore diameter distribution of a macromolecular filter membrane is wide, the pollution resistance is poor, and the membrane cannot be suitable for automatically adjusting the selectivity and the permeability, and realizes the regulation and control of the pH to the pore diameter of the filter membrane by grafting the pH-responsive polymer through ATRP. In addition, the amphiphilic graft copolymer is adopted to prepare the membrane by self-assembly, so that the hydrophilic modification and uniform pore diameter of the membrane are realized.
The above-described embodiments are merely preferred embodiments of the present invention, which should not be construed as limiting the invention. Various changes and modifications may be made by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present invention. Therefore, the technical scheme obtained by adopting the mode of equivalent replacement or equivalent transformation is within the protection scope of the invention.

Claims (11)

1. A preparation method of an amphiphilic graft copolymer mesoporous ultrafiltration membrane with pH response is characterized in that a hydrophobic polymer is used as a framework, the hydrophobic polymer is P (VDF-CTFE), the pH response polymer is prepared by ATRP grafting monomers, and the amphiphilic graft copolymer mesoporous ultrafiltration membrane with pH response is prepared by a non-solvent phase inversion method; the preparation method comprises the following steps:
dissolving a hydrophobic polymer, a monomer, a catalyst and a ligand into a first polar solvent to form a solution, wherein the ratio of the hydrophobic polymer to the monomer is 1: 2.6(g/m), the mass ratio of hydrophobic polymer to catalyst is 1:0.13, the volume ratio of monomer to ligand is 2.6:0.29, then, ensuring anhydrous and anaerobic conditions through three circulation operations of vacuumizing and nitrogen introduction, heating to 55-95 ℃, stirring for 4-24 hours, then diluting the solution to be non-viscous to obtain a polymer solution, dropwise adding the polymer solution into a methanol-water mixed solution with the volume of 1:1 for precipitation, filtering, collecting the precipitate, freeze-drying to constant weight to obtain P (VDF-CTFE) -g-PtBMA, then adding P (VDF-CTFE) -g-PtBMA into toluene solution containing 10 percent of P-toluenesulfonic acid by mass, mechanically stirring at 85 deg.C for 10 hr, hydrolyzing thoroughly, pouring the mixture into water, filtering, vacuum freeze-drying to constant weight to obtain P (VDF-CTFE) -g-PMAA with pH response;
dissolving P (VDF-CTFE) -g-PMAA with the mass fraction of 12-18% in a second polar solvent, heating and stirring at 60 ℃ for 12-24 h, standing and defoaming to obtain a homogeneous casting solution; pouring the casting film liquid onto a dry and clean glass plate uniformly, scraping a liquid film with a scraper at a constant speed, immersing the liquid film into a coagulating bath, preparing a pH response pore-equalizing filter film by a non-solvent induced phase transition method, periodically changing water to remove the solvent, and immersing the prepared film in distilled water for later use.
2. The preparation method of the amphiphilic graft copolymer homogeneous-pore ultrafiltration membrane with pH response of claim 1, wherein the catalyst is CuCl, CuBr or CuCl 2 、CuBr 2 Or a mixture thereof.
3. The preparation method of the amphiphilic graft copolymer mesoporous ultrafiltration membrane with pH response of claim 2, wherein the catalyst is CuCl.
4. The preparation method of the amphiphilic graft copolymer mesoporous ultrafiltration membrane with pH response of claim 1, wherein the first polar solvent is one of N-methylpyrrolidone, N-dimethylformamide, N, N-dimethylacetamide and dimethyl sulfoxide or a mixed solvent thereof.
5. The preparation method of the amphiphilic graft copolymer mesoporous ultrafiltration membrane with pH response of claim 4, wherein the first polar solvent is N-methylpyrrolidone.
6. The method for preparing the amphiphilic graft copolymer mesoporous ultrafiltration membrane with pH response of claim 1, wherein the ligand is one of N, N, N '' -pentamethyldiethylenetriamine and tris- (N, N-dimethylaminoethyl) amine or a mixture thereof.
7. The method for preparing the amphiphilic graft copolymer mesoporous ultrafiltration membrane with pH response of claim 6, wherein the ligand is N, N, N '' -pentamethyldiethylenetriamine.
8. The method for preparing the amphiphilic graft copolymer mesoporous ultrafiltration membrane with pH response of claim 1, wherein the second polar solvent is one of N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and tetrahydrofuran or a mixture thereof.
9. The preparation method of the amphiphilic graft copolymer mesoporous ultrafiltration membrane with pH response of claim 1, wherein the second polar solvent is N, N-dimethylformamide.
10. An amphiphilic graft copolymer mesoporous ultrafiltration membrane with pH response prepared based on the preparation method of any one of claims 1-9.
11. The application of the amphiphilic graft copolymer macroporous ultrafiltration membrane with pH response based on the claim 10 in the fields of pollutant fractional interception and water treatment, wherein pollutants are homopolystyrene and polyvinylpyrrolidone.
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